Reaction products of amic acids and primary aliphatic amines with alkylene polyamines and salicylaldehyde



United States Patent Divided and this application Mar. 12, 1964, Ser.No.

9 Claims. (Cl. 260-559) The present invention is a division of ourcopending application Ser. No. 181,164, filed Mar. 20, 1962, now PatentNo. 3,236,613, issued Feb. 22, 1966 and relates to petroleum hydrocarbondistillate fuel compositions containing a novel addition agent. Moreparticularly, the invention relates to novel chemical compounds that areuseful as anti-screen clogging and sediment stabilizing addition agentsfor petroleum hydrocarbon distillate fuel oils and, as anti oxidants andmetal deactivators in both fuel oils and gasolines.

As is known to those skilled in the art, virtually all gasolines,particularly those manufactured by pyrolytic processes such as crackingand polymerizatiomhave a tendency to form polymeric materials duringstorage and which materials are commonly known as gum. When present ingasoline, the gum forms resin-like deposits in the carburetor, intakemanifold and valve stems of internal combustion engines. Obviously, suchdeposits are objectionable because they decrease the efficiency of theengine and operational life.

It is also well known that petroluem hydrocarbon distillate fuel oilshave a tendency to deteriorate in storage and to form sludge. Suchsludge, together with other impurities present in stored fuels, such asrust, dirt and moisture, cause the formation of insoluble products thatsettle out of the fuel and adhere to the surfaces with which they comein contact with eventual clogging of equipment parts such as the screenand filters of burners and engines utilizing the fuel oil.

It has now been found that, by addition to such petroleum hydrocarbondistillates of novel condensation prod ucts as defined more fullyhereinafter, the aforesaid objectionable features of such distillatesare obviated or markedly decreased.

In generic aspect, the present invention is directed to petroleumdistillate hydrocarbon fuels containing from between about 1 to about100 pounds, per thousand barrels of fuel, of a compound'of the followingformula:

wherein R is the aliphatic residue of an aliphatic dicarboxylic acid, Ris an aliphatic hydrocarbon group, R" is a member from the groupconsisting of HNCHzCHZ and HNCH-CHz and x is an integer of from 1 to 6.

Such compounds of the foregoing formula can be prepared by, for example,heating at 75 to 110 C. for about 2 hours a mole to mole mixture of analiphatic dicarboxylic 3,336,384 Patented Aug. 15, 1967 acid anhydrideand aliphatic primary amine to form the amic acid, i.e.,

subjecting the amic acid (A) to condensation reaction at C. to C. for 2to '5 hours with a polyamine of the following formula:

H(R") NH in substantially molar amounts to provide the followingcondensation reaction product when the dicarboxylic acid is succinic,the final product has the formula:

II C CHHHHWNICHO and when the dicarboxylic acid is an alkenyl succinicacid anhydride, the final product has the formula:

or mixtures thereof, wherein R is the alkenyl group of the alkenylsuccinic anhydride.

In further reference to such compounds useful for the purposesaforedescribed, the aliphatic radical R can be the residue of any of awide variety of aliphatic dicarboxylic acid or anhydrides includingsaturated acid anhydrides such as succinic acid anhydride, unsaturatedacid anhydrides such as maleic acid anhydride, branch chain acidanhydrides such as the alkenyl succinic acid anhydride, specificallytetrapropenyl succinic acid anhydride, and others. Thus, inclusive ofsuch acids are aliphatic dicarboxylic acids in which the radical Rcontains from 2 to 18 carbon atoms and, of such acids, preferred are thealkenyl substituted-succinic andmaleic acids in which the alkenyl groupcontains from 3 to 16 carbon atoms.

For the radical R, which is an aliphatic group, attached to the nitrogenatom, such a radical can be provided in the aforesaid structurallydefined compounds by use of a relatively high molecular weight aliphaticprimary amine for the reaction with the dicarboxylic acid to prepare theintermediate amic acid, said amine being preferably characterized byhaving its nitrogen atom directly linked to a tertiary carbon atom.Preferably, the aliphatic radical R is provided as a result of use, forthe amic acid-forming reaction, of aliphatic primary amines having atertiary carbon atom as aforesaid and in which the aliphatic group hasfrom about 8 to 24 carbon atoms. Such an aliphatic group can besaturated or unsaturated. Moreover, for preparation of the novelcompounds embodied for use herein, the amic acid-forming reaction can becarried out by use of a mixture of aliphatic primary amines. Forpurposes of illustration and not limitation, examples of such aminesinclude t-dodecyl primary amine, t-tetradecyl primary amine,t-pentadecyl primary amine, t-hexadecyl primary amine, t-octadecylprimary amine, t-eicosyl primary amine, t-tetracosyl primary amine, andt-triacontyl primary amine whereby the R in the final product, useful asthe addition agent for petroleum distillates is the aliphatic radical ofthe particular primary amine or mixture of primary amines employed inthe amic acid-forming reaction.

Additional examples of amines include the n-aliphatic primary amines inwhich the aliphatic group contains from. about 8 to about 24 carbonatoms and, more specifically, n-octyl amine, n-dodecyl amine, and thelike. However, for provision of the group R, it is particularlypreferred that it be derived from a primary aliphatic amine in which thealiphatic group R has a t-carbon atom as the presence of a t-carbon atomattached to the nitrogen atom provides addition agents that inhibitemulsification as compared to use of corresponding compounds but inwhich R is a n-aliphatic group.

For the condensation reaction to provide intermediate (B) by reaction ofthe amic acid with a polyamine, the polyamine reactant is an alkylenepolyamine of the formula I-I(R") NH wherein R is a member from the groupconsisting of and x is an integer of 1 to 6. For such a purpose,suitable alkylene polyamines include ethylenediamine, propylenedia-mine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine andothers.

The distillate fuels that are improved in accordance with the presentinvention are the petroleum. distillates that include fuel oils andaviation and motor gasoline. The distillate fuel oils are hydrocarbonfractions having an initial boiling point of at least about 100 F. andan end-boiling point no higher than about 750 F., and boilingsubstantially continuously throughout their distillation range. Suchfuel oils are generally known as distillate fuel oils. It is to beunderstood, however, that this term is not restricted to straight-rundistillate fractions. The distillate fuel oils can be straight-rundistillate fuel oils, catalytically or thermally cracked (includinghydrocracked) distillate fuel oils, or mixtures of straight-rundistillate fuel oils, naphthas, and the like, with cracked distillatestocks. Moreover, such fuel oils can be treated in accordance with wellknown commercial methods, such as, acid or caustic treatment,hydrogenation, solvent refining, clay treatment, etc.

The distillate fuel oils are characterized by their relatively lowviscosities, pour points, and the like. The principal property whichcharacterizes the contemplated hydrocarbons, however, is thedistillation range. As mentioned hereinbefore, this range will liebetween about 100 F. and about 750 F. Obviously, the distillation rangeof each individual fuel oil will cover a narrower boiling range falling,nevertheless, within the above-specified limits. Likewise, each fuel oilwill boil substantially continuously throughout its distillation range.

Particularly contemplated among the fuel oils are Nos. 1, 2, and 3 fueloils used in heating and as Diesel fuel oils, and the jet combustionfuels. The domestic fuel oils generally conform to the specificationsset forth in ASTM Specifications D396-48T. Specification for Dieselfuels are defined in ASTM Specifications D97548T. Typical jet fuels aredefined in Military Specification MIL-F5624B.

The gasolines are mixtures of hydrocarbons suitable for use in internalcombustion engines of the spark-ignition type. These fuels include bothmotor gasolines and aviation gasolines. In general, motor gasolines havean initial boiling point as low as about F. and an end-boiling point ashigh as about 440 F. and boil substantially continuously between theinitial boiling point and the endboiling point. Aviation gasolines, onthe other hand, are mixtures of hydrocarbons having an initial boilingpoint of about 80 F. and an end-boiling point of about 340 F., and boilsubstantially continuously between these points.

The amount of the reaction product of thi invention that is added to thedistillate fuels will vary between about one pound per thousand barrelsand about pounds per thousand barrels of fuel, preferably, between about3 and about 50 pounds per thousand barrels. In general, smaller amounts,in the order of 3 to 10 pounds, will be used in motor fuels than in fueloils. In the latter case, the concentration is generally on the order of10 to 50 pounds per thousand barrels.

It is contemplated that other addition agents can be included in thedistillate fuel compositions to improve other characteristics. Thus, forexample, there can be present foam inhibitors, ignition and burningquality improvers, scavengers, deicers, carburetor detergents, andpreignition agents. Examples of such additives are silicones,dinitropropane, amyl nitrate, metal sulfonates, lead tetraethyl,haloalkanes, phosphate esters, alcohols, and the like.

The following specific examples are for the purpose of illustratingpreparation of specific compounds for use as embodied herein foradditives that impart the aforesaid improvements to petroleumhydrocarbon distillate fuels. It should be understood, however, thatthis invention is not intended to be limited to the particular compoundsand fuels, or to the operations and manipulations specifically describedas other compounds and fuels can be used as those skilled in the artwill readily appreciate.

In the following examples, the amine designated Primene 81R is a mixtureof primary alkyl amines having the amino nitrogen directly attached to atertiary carbon atom with the number of carbon atoms varying from 12 to15; and Primene JMT is a similar amine mixture with the number of carbonatoms varying from 18 to 24.

EXAMPLE 1 A mixture of 49 gms. (0.5 mole) of maleic anhydride, 100 gms.(0.5 mole) of Primene 81R and 222 gms. of xylene was stirred at 95 C.for 2 hours to form the Primene 81R maleamic acid. The Primene 81Rmaleamic acid was diluted with 150 cc. of benzene. To the Primene 81Rmaleamic acid was added gradually at room temperature with stirring 30gms. (0.5 mole) of ethylenediamine followed by the addition of 61 gms.(0.5 mole) of salicylaldehyde. The mixture was refluxed at 94109 C. for3 hours and at C. until water stopped coming over (about 3 hours). Theamount of water collected during the reflux was 17 cc., theory 18 cc.The reaction product, crystallizing on standing, was diluted with 444gms. of xylene and filtered through Hyfio clay. The final product, whichcontained 75% xylene, was clear and fluid at room temperature.

Analysis.Percent N: Estimated, 2.36. Found, 2.49.

EXAMPLE 2 A mixture of 32.7 gms. /3 mole) of maleic anhydride, 100 gms.6 mole) of Primene JMT and 363 gms. of xylene as diluent was heated at95 C. for 2 hours with stirring to form the Primene JMT maleamic acid.The Primene JMT maleamic acid was diluted with 100 cc. of benzene. Tothe Primene JMT maleamic acid there was added at room temperature withstirring 20 gms. /3 mole) of ethylenediamine followed by the addition of40.7 gms. /3 mole) of salicylaldehyde. The mixture was refluxed at 95119C. for 2 hours at 132 C. for 2 hours. The reaction product,crystallizing at room temperature, was diluted with 181 gms. of xyleneand filtered through Hyflo clay. The final product, which contained 75%xylene, was clear and fluid at room temperature.

Analysis.Percent N: Estimated, 1.19. Found, 1.86.

EXAMPLE 3 A mixture of 49 gins. (0.5 mole) of maleic anhydride, 100 gms.(0.5 mole) of Primene 81R and 229 gms. of xylene as diluent was stirredat 95 C. for 2 hours to form the Primene 81R maleamic acid. The Primene81R maleamic acid was diluted with 100 cc. of benzene. To the Primene81R maleamic acid was added gradually at room temperature with stirring37 gms. (0.5 mole), equivalent to 43.5 gms. of 85% propylenediamine,followed by the addition of 61 gms. (0.5 mole) of salicylaldehyde. Themixture was refluxed at 95 C.118 C. for 2 hours and at 135 C. untilwater stopped coming over (about 2 hours). The amount of water collectedduring the reflux was 21 cc., theory 18 cc. The final product, whichcontained 50% xylene, was clear and fluid at room temperature.

Analysis.--Percent N: Estimated, 4.6. Found, 502.

EXAMPLE 4 A mixture of 49 gms. (0.5 mole) of maleic anhydride, 150 gms.(0.5 mole) of Primene JMT and 279 gms. of xylene as diluent was stirredat 95 C. for 2 hours to form the Primene J MT maleamic acid. The PrimeneJ MT maleamic acid was diluted with 150 cc. of benzene. To the PrimeneJMT maleamic acid was added gradually at room temperature with stirring37 gms. (0.5 mole), equivalent to 43.5 gms. of 85% propylenediamine,followed by the addition of 61 gms. (0.5 mole) of salicylaldehyde. Themixture was refluxed at 93-112" C. for 2 hours and at 135 C. until Waterstopped coming over (about 3 hours). The amount of water collectedduring the reflux was 21 cc., theory 18 cc. The reaction product wasfiltered through Hyflo clay. The final product, which contanied 50%xylene, was clear and fluid at room temperature.

Analysis.-Percent N: Estimated, 3.8. Found, 3.82.

EXAMPLE 5 A mixture of 32% gms.' /3 mole) of maleic anhydride, 66 /3gms. /s mole) of Primene 81R and 100 gms. of xylene was stirred at 8090C. for 2 hours to form the Primene 81R maleamic acid. The Primene 81Rmaleamic acid was diluted with 50 cc. of benzene. To the Primene 81Rmaleamic acid was added gradually at room temperature with stirring 34/3 gms. /3 mole) of diethylenetriamine followed by the addition of 40 /3gms. /3 mole) of salicylaldehyde. The mixture was refluxed at 100120 C.for 2 hours and at 150 C. until water stopped coming over (about 2hours). The amount of water collected during the reflux was 15 cc.,theory 12 cc. The reaction product which weighed 251 gms., theory 159gms., contained 92 gms. of xylene and was filtered through Hyflo clay.The final product, which contained 37% xylene, was clear and fluid atroom temperature.

Analysis.Percent N: Estimated, 7.5. Found, 7.09.

6 EXAMPLE 6 A mixture of 32 /3 gms. /a mole) of maleic anhydride, 115gms. mole+15 gms. excess) of Primene JMT and 100 gms. of xylene asdiluent was stirred at 90 C. for 2 hours to form the Primene JMTmaleamic acid. The Primene JMT maleamic acid was diluted with 50 cc. ofbenzene. To the Primene JMT maleamic acid was added gradually at roomtemperature with stirring 34% gms. (93 mole) of diethylenetriaminefollowed by the addition of 40 /3 gms. /3 mole) of salicylaldehyde. Themixture was refluxed at 120 C. for 2 hours and at 155 C. until waterstopped coming over (about 2 hours). The amount of water collectedduring the reflux was 15 cc., theory 12 cc. The reaction product whichweighed 302 gms., theory 208 gms. contained 94 gms. of xylene and wasfiltered through Hyflo clay. The final product, which contained 31%xylene, was clear and fluid at room temperature.

Analysis.Percent N: Estimated 6.2. Found, 6.71.

EXAMPLE 7 A mixture of 32 /3 gms. /3 mole) of maleic anhydride, 66% gms.(Va mole) of Primene 81R and 100 gms. of xylene as diluent was stirredat 80-90 C. for 2 hours to form the Primene 81R maleamic acid. ThePrimene 81R maleamic acid was diluted with 50 cc. of benzene. To thePrimene 81R maleamic acid was added gradually at room temperature withstirring 48% gms. /a mole) of triethylene-tetramine followed by theaddition of 40 /3 gms. /3 mole) of salicylaldehyde. The mixture wasrefluxed at 100-122 C. for 2 hours and at 150 C. until water stoppedcoming over (about 2 hours).

The amount of water collected was 15 cc., theory 12 cc.

EXAMPLE 8 A mixture of 32 /3 gms. mole) of maleic anhydride, gms. /3mole) |-15 gms. excess of Primene JMT and 100 gms. of xylene as diluentwas stirred at 80-90 C. for 2 hours to form the Primene JMT malearnicacid. The Primene JMT maleamic acid was diluted with 50 cc. of benzene.To the Primene JMT maleamic acid was added gradually at room temperaturewith stirring 49 /3 gms. /3 mole) of triethylene-tetramine followed bythe addition of 40% gms. /3 mole) of salicylaldehyde. The mixture wasrefluxed at 100-123 C. for 2 hours and at 153 C. until water stoppedcoming over (about 2 hours). The amount of water collected during thereflux was 15 cc., theory 12 cc. The reaction product which weighed 304gms., theory 222 gms., contained 84 gms. of xylene and was filteredthrough Hyflo clay. The final product, which contained 28% xylene, wasclear and fluid at room temperature.

Analysis.Percent N: Estimated, 7.6. Found, 7.36.

EXAMPLE 9 A mixture of 32 /3 gms. /s mole) of maleic anhydride, 66% gms./3 mole) of Primene 81R and 100 gms. of xylene was stirred at 8090 C.for 2 hours to form the Primene 81R maleamic acid. The Primene 81Rmaleamic acid was diluted with 50 cc. of benzene. To the Primene 81Rmaleamic acid was added gradually at room temperature with stirring 63gms. /3 mole) of tetraethylenepentamine followed by the addition of 40/3 gms. /3 mole) of salicylaldehyde. The mixture was refluxed at 100-125C. for 2 hours and at -155 C. until water stopped coming over (about 4hours). The amount of water collected during the reflux was 14 cc.,theory 12 cc. The reaction product which weighed 266 gms., theory 189gms., contained 77 gms. of xylene and was filtered through Hyflo clay.The final product, which 7 contained 29% xylene, was clear and fluid atroom temperature.

AnaIysis.-Percent N: Estimated, 10.5. Found, 10.33.

EXAMPLE A mixture of 32 /3 gms. /a mole) of maleic anhydride, 115 gms./3 mo1e+l5 gms. excess) of Primene JMT and 100 gms. of xylene wasstirred at 8090 C. for 2 hours to form the Primene J MT maleamic acid.The Primene JMT maleamic acid was diluted with 50 cc. of benzene. To thePrimene J MT maleamic acid was added gradually at room temperature withstirring 63 gms. /3 mole) of tetraethylenepentamine followed by theaddition of 40% gms. /3 mole) of salicylaldehyde. The mixture wasrefluxed at 100-125 C. for 2 hours and at 155 C. until water stoppedcoming over (about 4 hours). The amount of water collected during thereflux was cc., theory 12 cc. The reaction product, which weighed 320gms., theory 237 gms., contained 83 gms. of xylene and was filteredthrough Hyflo clay. The final product, which contained 26% xylene, wasclear and fluid at room temperature.

AnaIysis.Percent N: Estimated 8.7. Found, 8.24.

EXAMPLE 1 1 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Primene 81R, 100 cc. of xylene and 150 cc. of benzenewas stirred at 95 C. for 2 hours to form the Primene 81R succinamicacid. The the Primene 81R succinamic acid was added gradually at roomtemperature with stirring 30 gms. (0.5 mole) of ethylenediamine followedby the addition of 61 gms. (0.5 mole) of salicylaldehyde. After themixture had been refluxed at 95 C. for 2 hours, the temperature was thengradually raised to 150 C. and was held at 150 C. until water stoppedcoming over (about 2 hours). The amount of water collected during thereflux Was 18 cc., theory 18 cc. The reaction product, which weighed 321gms., theory 223 gms., contained 98 gms. of xylene. The reactionproduct, crystallizing at room temperature, was diluted with 223 gms. ofxylene and 348 gms. of isopropanol. The final product which contained75% solvent (36% xylene+39% isopropanol) was clear and fluid at roomtemperature.

Analysis.Percent N: Estimated, 2.3. Found, 2.23.

EXAMPLE 12 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Primene J MT and 100 cc. xylene was stirred at 95 C.for 2 hours to form the Primene J MT succinamic acid. The Primene J MTsuccinamic acid was diluted with 150 cc. of benzene. To the Primene J MTsuccinamic acid was added gradually at room temperature with stirring 30gms. (0.5 mole) of ethylenediamine followed by the addition of 61 gms.(0.5 mole) of salicylaldehyde. After the mixture had been refluxed at 95C. for 2 hours, the mixture was gradually heated to 165 C. and was heldat 165 C. until water stopped coming over (about 2 hours). The amount ofwater collected during the reflux was 18 cc., theory 18 cc. The reactionproduct, crystallizing at room temperature, was diluted with 273 gms. ofxylene and 273 gms. of isopropanol. The final product, which contained66 /3% solvent (33 /s% xylene+33 /s% isopropanol), was clear and fluidat room temperature.

Analysis.-Percent N: Estimated, 2.5. Found, 2.79.

EXAMPLE 13 A mixture of 33% gms. (Va mole) of succinic anhydride, 66 /3gms. /3 mole) of Primene 81R and 306 gms. of xylene as diluent wasstirred at 95 C. for 2 hours to form the Primene 81R succinamic acid.The Primene 81R succinamic acid was diluted with 100 cc. of benzene. Tothe Primene 81R succinamic acid was added gradually at room temperaturewith stirring 24 /3 gms. /3 mole), equivalent to 29 gms. of 85%propylenediamine, followed by the addition of 40 /3 gms. (Vs mole) ofsalicylaldehyde.

After the mixture had been refluxed at l02ll7 C. for 2 hours, themixture was gradually heated to 130 C. and was held at 130 C. untilwater stopped coming over (about 3 hours). The amount of water collectedduring the reflux was 15 cc., theory 16 cc. The reaction product, whichcontained 66 /a% xylene, was clear and fluid at room temperature.

Arzalysis.Percent N: Estimated, 3.04. Found, 3.36.

EXAMPLE 14 A mixture of 33 /3 gms. /3 mole) of succinic anhydride, 100gms. mole) of Primene JMT and 187 gms. of xylene as diluent was stirredat C. for 2 hours to form the Primene JMT succinamic acid. The Primene JMT succinamic acid was diluted with cc. of benzene. To the Primene J MTsuccinamic acid was added gradually at room temperature with stirring 24/3 gms. /a mole), equivalent to 29 gms. of 85% propylenediamine,followed by the addition of 40 /3 gms. /3 mole) of salicylaldehyde.After the mixture had been refluxed at -110 C. for 2 hours, the mixturewas gradually heated to 155 C. and was held at 155 C. until waterstopped coming over (about 3 hours). The amount of water collectedduring the reflux was 16 cc., theory 16 cc. The reaction product wasfiltered through Hyflo clay. The final product, which contained 66 /a%xylene, was clear and fluid at room temperature.

Analysis.Percent N: Estimated, 4.9. Found, 5.29.

EXAMPLE 15 A mixture of 33 /3 gms. /3 mole) of succinic anhydride, 66%gms. /3 mole) of Primene 81R and 163 gms. of xylene was stirred at 95 C.for 2 hours to form the Primene 81R succinamic acid. The Primene 81Rsuccinamic acid was added gradually at room temperature with stirring 34/3 gms. /a mole) of diethylenetriamine followed by the addition of 40 /3gms. /a mole) of salicylaldehyde. The mixture, after having beenrefluxed at 100-110 C. for 2 hours, was gradually heated to C. and washeld at 125 C. until water stopped coming over (about 3 hours). Theamount of water collected during the reflux was 13 cc., theory 12 cc.The reaction product was filtered through Hyflo clay. The final product,which contained 50% xylene, was clear and fluid at room temperature.

Analysis.-Percent N: Estimated, 5.7. Found, 5.63.

EXAMPLE 16 A mixture of 33 /3 gms. /a mole) of succinic anhydride, 100gms. mole) of Primene J MT and 100 gms. of xylene as diluent was stirredat 95 C. for 2 hours to form the Primene JMT succinamic acid. ThePrimene J MT succinamic acid was diluted with 50 cc. of benzene. To thePrimene J MT succinamic acid was added gradually at room temperaturewith stirring 34 /3 gms. mole) of diethylenetriamine followed by theaddition of 40 /3 gms. /3 mole) of salicylaldehyde. The mixture, afterhaving been refluxed at l10125 C. for 3 hours, was gradually heated toC. and was held at 150 C. for 3 hours. The amount of water collectedduring the reflux was 17 cc., theory 12cc. The reaction product whichcontained 26% xylene was filtered through Hyflo clay. The final productwas clear and fluid at room temperature.

Analysis-Percent N: Estimated, 6.6. Found, 6.49.

EXAMPLE 17 A mixture of 33 /3 gms. /a mole) of succinic anhydride, 66%gms. /s mole) of Primene 81R and 100 gms. of xylene as diluent wasstirred at 95 C. for 2 hours to form the Primene 81R succinamic acid wasdiluted with 50 cc. of benzene. To the Primene 81R succinamic acid wasadded gradually at room temperature with stirring 48% gms. /a mole) oftriethylenetetramine followed by the addition of 40 /3 gms. (/3 mole) ofsalicylaldehyde. After the mixture had been refluxed at 125- 9 135 C.for 4 hours, the temperature was gradually raised to 150 C. and was heldat 150 C. until water stopped coming over (about 3 hours). The amount ofwater collected during the reflux was 16 cc., theory 12 cc. The reactionproduct, weighing 255 gms., theory 177 gms., contained 78 gms. ofxylene. The final product which contained 30% xylene was clear and fluidat room temperature.

Analysis-Percent N: Estimated, 90. Found, 8.69.

EXAMPLE 18 A mixture of 33 /3 gms. /a mole) of succinic anhydride, 115gms. /3 mole-lgms. excess) of Primene JMT and 100 cc. of xylene asdiluent was stirred at 95 C. for 2 hours to form the Primene I MTsuccinamic acid. The Primene JMT succinamic acid was diluted with 50 cc.of benzene. To the Primene 1 MT succinamic acid was added gradually atroom temperature with stirring 48 /3 gms. /s mole) oftriethylenetetramine followed by the addition of 40 /3 gms. /s mole) ofsalicylaldehyde. The mixture was refluxed at 125 C. for 3 hours and at145 C. for 2 hours. The amount of water collected during the reflux was16 cc., theory 12 cc. The reaction product, which weighed 306 gms.,theory 222 gms., and contained 84 gms. of xylene was filtered throughHyflo clay. The final product, which contained 27.5% xylene, was clearand fluid at room temperature.

Analysis-Percent N: Estimated, 7.5. Found, 7.18.

I EXAMPLE 19 A mixture of 33 /3 gms. /3 mole) of succinic anhydride, 66/3 gms. /3 mole) of Primene 81R and 100 gms. of xylene as diluent wasstirred at 95 C. for 2 hours to form the Primene 81R succinamic acid.The Primene 81R succinamic acid was diluted with 50 cc. of benzene. Tothe Primene 81R succinamic acid was added gradually at room temperaturewith stirring 63 gms. /3 mole) of tetraethylenepentamine followed by theaddition of 40 /3 gms. /3 mole) of salicylaldehyde. The mixture wasrefluxed at 130-135 C. for 4 hours and at 150 C. for 3 hours. The amountof water collected during the reflux was 16 cc., theory 12 cc. Thereaction product, which weighed 268 gms. theory 190 gms., and contained78 gms. of xylene was filtered through Hyflo clay. The final product,which contained 28% xylene, was clear and fluid at room temperature.

Analysis.-Percent N: Estimated, 10.4. Found, 9.9.

EXAMPLE A mixture of 33 /3 gms. /s mole) of succinic anhydride, 115 gms.(Va mole+15 gms. excess) of Primene JMT and 100 gms. of xylene asdiluent was stirred at 95 C. for 2 hours to form the Primene JMTsuccinamic acid. The Primene J MT succinamic acid was diluted with 50cc. of benzene. To the Primene JMT succinamic acid was added graduallyat room temperature with stirring 63 gms. (Vs mole) oftetraethylenepentamine followed by the addition of 40% gms. (Vs mole) ofsalicyladehyde. The mixture was refluxed at 125 C. for 3 hours and at145 C. for 2 hours. The amount of water collected during the reflux was16 cc., theory 12 cc. The reaction product which weighed 319' gms.,theory 236 gms., contained 83 gms. of xylene was filtered through Hyfloclay. The final product, which contained 26% xylene, was clear and fluidat room temperature.

Analysis.Percent N: Estimated, 8.8. Found, 8.41.

EXAMPLE 21 A mixture of 133 gms. (0.5 mole) tetrapropenylsuccinicanhydride, 100 gms. (0.5 mole) of Primene 81R and 150 cc. of xylene wasstirred at 95 C. for 2 hours to form the Primene 81Rtetrapropenylsuccinamic acid. The Primene 81R tetrapropenylsuccinamicacid was diluted with 100 cc. of benzene. To the Primene 81Rtetrapropenylsuccinamic acid was added gradually at room temperaturewith stirring 30 gms. (0.5 mole) of ethylenediamine followed by theaddition of 61 gms. (0.5 mole) of salicylaldehyde. The mixture wasrefluxed at 95105 C. for 2 hours, 150 C. for 2 hours, and 175 C. for 2hours. The amount of water collected during the reflux was 24 cc.,theory 18 cc. The reaction product which weighed 345 gms., theory 301gms., contained 44 gms. (13%) xylene. The reaction product was thendiluted with 128 gms. (37%) isopropanol. The final product, whichcontained 50% solvent (13% xylene+37% isopropanol), was clear at roomtemperature.

Analysis.Percent N: Estimated, 3.5. Found, 4.0.

EXAMPLE 22 A mixture of 133 gms. (0.5 mole) of tetrapropenylsuccinicanhydride, 150 gms. (0.5 mole) of Primene JMT and 100 cc. of xylene asdiluent was stirred at 95 C. for 2 hours to form the Primene JMTtetrapropenylsuccinamic acid. The Primene JMT tetrapropylenylsuccinamicacid was diluted with 150 cc. of benzene. To the Primene JMTtetrapropenylsuccinamic acid was added gradually at room temperaturewith stirring 30 gms. (0.5 mole) of ethylenediamine followed by theaddition of 61 gms. (0.5 mole) of salicylaldehyde. The mixture wasrefluxed at 95-105 C. for 2 hours, 150 for 2 hours and 175 C. for 3hours. The amount of water collected during the reflux was 23 cc.,theory 18 cc. The finished product which weighed 376 gms., theory 352gms., and contained 6.5% xylene was clear and fluid at room temperature.

Analysis.-Percent N: Estimated, 5.5. Found, 4.9.

EXAMPLE 23 i A mixture of 133 gms. (0.5 mole) of tetrapropenylsuccinicanhydride, 100 gms. (0.5 mole) of Primene 81R and 150 cc. of xylene wasstirred at 95 C. for 2 hours to form the Primene 81Rtetrapropenylsuccinamic acid. The Primene 81R tetrapropenylsuccinamicacid was diluted with 75 cc. of benzene. To the Primene 81Rtetrapropenylsuccinamic acid was added gradually at room temperaturewith stirring 37 gms. (0.5 mole), equivalent to 43.5 gms. ofpropylenediamine, followed by the addition of 61 gms. (0.5 mole) ofsalicylaldehyde. After the mixture had been refluxed at 100 C. for 2hours, the temperature was gradually raised to 150 C. and held for 2hours at 150 C. and 175 C. for 2 hours. The amount of water collectedduring the reflux was 24.5 cc., theory 24.5 cc. The reaction productwhich weighed 382 gms., theory 308 gms., and contained 74 gms. (19.5%)xylene was clear and fluid at room temperature.

Analysis.Percent N: Estimated, 5.5. Found, 5.24.

EXAMPLE 24 A mixture of 133 gms. (0.5 mole) of tetrapropenylsuccinicanhydride, 150 gms. (0.5 mole) of Primene JMT and 181 gms. of xylene asdiluent was stirred at C. for 2 hours to form the Primene JMTtetrapropenylsuccinamic acid. The Primene JMT tetrapropenylsuccinamicacid wan diluted with cc. of benzene. To the Primene JMTtetrapropenylsuccinamic acid was added gradually at room temperaturewith stirring 37 gms. (0.5 mole), equivalent to 46 gms. of 80%propylenediamine, followed by the addition of 61 gms. (0.5 mole) ofsalicylaldehyde. The mixture was refluxed at 100 C. for 3 hours, thengradually heated to C. and held at 140 C. until water stopped comingover (about 2 hours). The reaction product was filtered through Hyfloclay. The final product which contained approximately 33%% xylene wasclear and fluid at room temperature.

Analysis.Percent N: Estimated, 4.0; Found: 4.15.

EXAMPLE 25 A mixture of 133 gms. (0.5 mole) of tetrapropenylsuccinicanhydride, 100 gms. (0.5 mole) of Primene 81R and cc. of xylene wasstirred at 95 C. for 2 hours to form the Primene 81Rtetrapropenylsuccinamic acid.

To the Primene 81R tetrapropenylsuccinamic acid Was added gradually atroom temperature with stirring 51.5 gms. (0.5 mole) ofdiethylenetriamine followed by the addition of 61 gms. (0.5 mole) ofsalicylaldehyde. The mixture was refluxed at 150 C. for 3 hours, thengradually heated to 175 C. and held at 175 C. until water stopped comingover (about 2 hours). The amount of water collected during the refluxWas 22 cc., theory 18 cc. The reaction product which weighed 373 gms.,theory 323 gms., contained 40 gms. (14%) xylene and Was clear and fluidat room temperature.

Azmlysis.Percent N: Estimated 7.5. Found 7.26.

EXAMPLE 26 A mixture of 133 gms. (0.5 mole) of tetrapropenylsuccinicanhydride, 150 gms. (0.5 mole) of Primene JMT and 150 cc. of xylene wasstirred at 95 C. for 2 hours to form the Primene JMTtetrapropenylsuccinamic acid. To the Primene J MTtetrapropenylsuccinamic acid was added gradually at room temperaturewith stirring 51.5 gms. (0.5 mole) of diethylenetriamine followed by theaddition of 61 gms. (0.5 mole) of salicylaldehyde. The mixture wasrefluxed at 150 C. for 3 hours and at 165 C. until water stopped comingover (about 2 hours). The amount of water collected during the refluxwas 19 cc., theory 18 cc. The reaction product which weighed 446 gms.,theory 373 gms., and contained 73 gms. (17%) xylene was clear and fluidat room temperature.

Analysis.-Percent N: Estimated 6.3. Found 5.96.

EXAMPLE 27 A mixture of 133 gms. (0.5 mole) of tetrapropenylsuccinicanhydride, 100 gms. (0.5 mole) of Primene 81R and 150 cc. of xylene asdiluent was stirred at 95 C. for 2 hours to form the Primene 81Rtetrapropenylsuccinamic acid. To the Primene 81R tetrapropenylsuccinamicacid was added gradually at room temperature with stirring 73 gms. (0.5mole) of triethylenetetramine 1 2 EXAMPLE 23 A mixture of 133 gms. (0.5mole) of tetrapropenylsuccinic anhydride, 100 gms. (0.5 mole) of Primene81R and 150 cc. of toluene was stirred at 95 C. for 2 hours to form thePrimene 81R tetrapropenylsuccinamic acid. To the Primene 81Rtetrapropenylsuccinamic acid was added gradually at room temperaturewith stirring 94.5 gms. (0.5 mole) of tetraethylenepentamine followed bythe addition of 61 gms. (0.5 mole) of salicylaldehyde. The mixture wasrefluxed at 150 C. for 3 hours, then gradually heated to 175 C. and heldat 175 C. until water stopped coming over (about 2 hours). The amount ofwater collected during the reflux was 22 cc., theory 18 cc. The reactionproduct which weighed 400 gms., theory 366 gms., and contained 34 gms.(9%) toluene was clear and fluid at room temperature.

Analysis.Percent N: Estimated 10.5. Found 9.86.

The effectiveness of the aforesaid products for improving the propertiesof petroleum hydrocarbon distillate fuels is demonstrated in thefollowing tests:

Gasoline storage tests A test procedure to determine storage stabilityis the 110 F. Gasoline Storage Test. Into each of two one-half gallonamber glass jugs (for duplicate samples) are placed 1200 ml. of thegasoline under test. The jugs are then capped tightly with foil-linedscrew caps. Then, they are stored at 110 F. for a number of weeks(usually 15-30 weeks). In order to gauge the effectiveness of aninhibited gasoline, the test gasoline is cooled to F. and a sample istaken at the end of the storage period. The ASTM gum content isdetermined (ASTM Test D381). The value obtained is compared with theASTM gum content of the uninhibited base gasoline.

Pertinent data and results obtained from use of compounds prepared inthe foregoing examples are set forth in Table I.

TABLE I.GASOLINE STORAGE TESTS [Inhibitors blended in a gasoline blendcomprising 100% catalytically cracked component approximately IOU-400 F.boiling range, and containing 3 ec./gal. oi tetraethyl lead] Cone. ofASTM Gum Inhibitor Inhibitor, Weeks at Increase,

lbs/1,000 bbls. 110 F. mg./100 ml.

of gasoline Uninhibited gasoline 0 26 27. 6 Do 5 26 5. 5 0 2G 27. 6 5 264. 3 0 2G 27. 6 5 26 4. 7 0 26 27. 6 5 26 4. 3 0 16 55. 0 5 16 2.8 0 1816.2 3 18 3. 7 0 16 55. 0 5 1G 4. 4 0 1G 55. O 5 16 4. 2 0 18 50. 9 5 184. 1 0 18 50. 9 5 18 3. 9

Gasoline Storage Test with copper A more severe storage test is theStorage Test with copper. This test is carried out in the same manner asthe 110 F. Storage Test except that a copper compound which serves tocatalyze oxidation to form gum, is added to the gasoline.

Pertinent data and results obtained from use of the compounds preparedin the foregoing examples are set forth in Table II.

TABLE II.-GASOLINE STORAGE TEST WITH COPPER {Inhibitors blended in agasoline blend comprising 100% catalytically crackedcomponentapproximately 100-400" F. boiling range] Inhibitor ASTM GumInhibitor Weeks at Cone, lbs./ Increase,

100 F. 1,000 bbls. ing/100 ml.

Uninhibited gasoline-F3 cc. TEL/ 17 118 gal.+0.2 mg. copper naphthenate/liter.

Fuel Oil Screen Clogging Test The anti-screen clogging characteristicsof a fuel oil were determined as follows: The test is conducted using aSundstrand V3 or S1 home fuel oil burner pump with a self-containedl00-mesh Monel metal screen. About 0.05 percent, by weight, ofnaturally-formed fuel oil sediment, composed of fuel oil water, dirt,rust, and organic sludge is mixed with 10 liters of the fuel oil. Thismixture is circulated by the pump through the screen for 6 hours. Then,the sludge deposit on the screen is washed off with normal pentane andfiltered through a tared Gooch crucible. After drying, the material inGooch crucible is washed with a 50-50 (volume) acetone-methanol mixture.The total organic sediment is obtained by evaporating the pentane andthe acetone-methanol filtrates. Drying and weighing the Gooch crucibleyields the amount of inorganic sediment. The sum of the organic andinorganic deposits on the screen can be reported in miligrams recoveredor converted into percent screen clogging.

Pertinent data and results obtained from use of compounds prepared inthe foregoing examples are set forth in Table III.

TABLE III.--SCREEN CL'OGGING TESTS [Inhibitors blended in a fuel oilblend comprising 60% catalytically cracked component and 40% straightrun componentapproximately 320-640 F. boiling range] Inhibitor concn.,lb./ 1,000 bbls.

Screen Clogging,

Inhibitor percent Uninhibited fuel blend. Do

Fuel Oil Storage Tests a tared asbestos filter (Gooch crucible) toremove insoluble matter. The weight of such matter in milligrams isreported as the amount of sediment. A sample of the blank, uninhibitedoil is run along with a fuel oil blend under test. The effectiveness ofa fuel oil containing an inhibitor is determined by comparing the weightof sediment formed in the inhibited oil with that formed in theuninhibited oil.

Pertinent data and results obtained from use of compounds prepared inthe foregoing examples are set forth in'Table IV.

TABLE IV.FUEL OIL STORAGE TESTS [Inhibitors blended in a fuel oil blendcomprising 60% catalytically cracked component and 40% straight runcomponentapproximately 320-640 F. boiling range] It is apparent from theforegoing that the compounds of this invention are effective inimparting highly desired improvements in fuel oils and gasolines.

Although the present invention has been described with preferredembodiments, it is to be understood that modifications and variationsmay be resorted to, without departing from the spirit and scope of thisinvention, as those skilled in the art will readily understand. Suchvariations and modifications are considered to be within the purview andscope of the appended claims.

15 What is claimed is: 1. A chemical compound of the following formula:

wherein R is an alkyl or alkenyl group of 2 to 18 carbon atoms, R is analkyl group of 8 to 24 carbon atoms, R" is a member from the groupconsisting of HNCI-IzCHz HNCH-CH:

and

in which the respective nitrogen atom of each group is attached to thecarbonyl groups and x is an integer of 20 from 1 to 6.

2. A compound, as defined in claim 1, wherein R has a tertiary carbonatom attached to the nitrogen atom.

16 3. A compound, as defined in claim 1, wherein R" is HNCH CH 4. Acompound, as defined in claim 1, wherein R" is rmoH-CH,

References Cited I UNITED STATES PATENTS 9/1953 Castillo et al. 2605 62x 8/1962 Gee et a1. 44-72 WALTER A. MODANCE, Primary Examiner.

N. TROUSOF, Assistant Examiner.

1. A CHEMICAL COMPOUND OF THE FOLLOWING FORMULA: